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A study of the transient (chronoamperometric) response of the scanning electrochemical microscope (SECM) is presented. SECM transients were simulated digitally with a novel integrator based on a Krylov algorithm. The transients observed with planar electrodes (PE), microdisks (MD), and thin-layer cells (TLC) are shown to be limiting cases that fit the simulated SECM transients at very short, intermediate, and long times, respectively. A procedure is established that, provided the tip radius is known, allows the determination of the diffusion coefficient of the species in solution independent of its concentration and the number of electrons transferred in the electrode reaction. Experimental SECM transients are reported for the electrochemical oxidation of Fe(CN)6(4-) in KCl; the diffusion coefficient of Fe(CN)6(4-) was found to agree very well with the literature value.

Soil hydraulic parameters used in estimating soil water and energy fluxes are included in a lookup table in the Noah Land Surface Model (LSM). The purpose of the study was to examine the Noah default soil hydraulic parameters and compare them to soil measurements across Texas, USA. These default soil parameters were compared to measured soil properties from a soil database including 6,749 soil samples located within and around Texas. Mean differences between measured and default soil parameters were tested using a t-test (α = 0.05). To assess the proposed changes to default soil parameters, water retention curves were created using updated parameters and compared to measured soil moisture content at field capacity (θ fc) and permanent wilting point (θ wp). Spatial trends across major land resource areas in Texas were also demonstrated for water retention parameters. Our findings indicate that 95% of the default soil parameters were significantly different from the region-specific measured values. Measured soil water content at air-dry, θ wp , and θ fc are better replacements than default values. Consequent changes in θ wp and θ fc yielded a 35 to 76% decrease in plant available water compared to default. Updated water retention curves showed improved agreement between estimated soil water and measured values in 95% of cases. For three texture classes, the standard deviations of parameters for water retention parameters ranged 30% for the slope of the water retention curve and 65% for saturated hydraulic conductivity. These results indicate the importance of accounting for spatial variability of soil parameters rather than combining these parameters into texture classes alone. The revised parameter table improves modeling of soil hydraulic properties. Ultimately spatially distributed databases of hydraulic soil parameters will better capture variability and spatial structure of soil processes modeled by Noah LSM.

[1] Clouds can significantly affect photochemical activities in the boundary layer by altering radiation intensity, and therefore their correct specification in the air quality models is of outmost importance. In this study we introduce a technique for using the satellite observed clouds to correct photolysis rates in photochemical models. This technique was implemented in EPA's Community Multiscale Air Quality modeling system (CMAQ) and was tested over a 10 day period in August 2000 that coincided with the Texas Air Quality Study (TexAQS). The simulations were performed at 4 and 12 km grid size domains over Texas, extending east to Mississippi, for the period of 24 to 31 August 2000. The results clearly indicate that inaccurate cloud prediction in the model can significantly alter the predicted atmospheric chemical composition within the boundary layer and exaggerate or underpredict ozone concentration. Cloud impact is acute and more pronounced over the emission source regions and can lead to large errors in the model predictions of ozone and its by-products. At some locations the errors in ozone concentration reached as high as 60 ppb which was mostly corrected by the use of our technique. Clouds also increased the lifetime of ozone precursors leading to their transport out of the source regions and causing further ozone production down-wind. Longer lifetime for nitrogen oxides (NO x = NO + NO 2 ) and its transport over regions high in biogenic hydrocarbon emissions (in the eastern part of the domain) led to increased ozone production that was missing in the control simulation. Over Houston-Galveston Bay area, the presence of clouds altered the chemical composition of the atmosphere and reduced the net surface removal of reactive nitrogen compounds. Use of satellite observed clouds significantly improved model predictions in areas impacted by clouds. Errors arising from an inconsistency in the cloud fields can impact the performance of photochemical models used for case studies as well as for air quality forecasting. Air quality forecast models often use the model results from the previous forecast (or some adjusted form of it) for the initialization of the new forecast. Therefore such errors can propagate into the future forecasts, and the use of observed clouds in the preparation of initial concentrations for air quality forecasting could be beneficial.

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